Stable Actinide π Complexes of a Neutral 1,4-Diborabenzene
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA..
The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d-block and f-block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora-π-aromatics are less prevalent particularly for the f-block, due to less effective metal-to-ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting the exceptionally strong π donor capabilities of a neutral 1,4-diborabenzene. A series of remarkably robust, π-coordinated thorium(IV) and uranium(IV) half-sandwich complexes were synthesized by simply combining the bora-π-aromatic with ThCl4 (dme)2 or UCl4 , representing the first examples of actinide complexes with a neutral boracycle as sandwich-type ligand. Experimental and computational studies showed that the strong actinide-heteroarene interactions are predominately electrostatic in nature with distinct ligand-to-metal π donation and without significant π/δ backbonding contributions.
Medienart: |
E-Artikel |
---|
Erscheinungsjahr: |
2020 |
---|---|
Erschienen: |
2020 |
Enthalten in: |
Zur Gesamtaufnahme - volume:59 |
---|---|
Enthalten in: |
Angewandte Chemie (International ed. in English) - 59(2020), 31 vom: 27. Juli, Seite 13109-13115 |
Sprache: |
Englisch |
---|
Beteiligte Personen: |
Paprocki, Valerie [VerfasserIn] |
---|
Links: |
---|
Themen: |
---|
Anmerkungen: |
Date Revised 12.11.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
---|
doi: |
10.1002/anie.202004501 |
---|
funding: |
|
---|---|
Förderinstitution / Projekttitel: |
|
PPN (Katalog-ID): |
NLM309134501 |
---|
LEADER | 01000naa a22002652 4500 | ||
---|---|---|---|
001 | NLM309134501 | ||
003 | DE-627 | ||
005 | 20231225133237.0 | ||
007 | cr uuu---uuuuu | ||
008 | 231225s2020 xx |||||o 00| ||eng c | ||
024 | 7 | |a 10.1002/anie.202004501 |2 doi | |
028 | 5 | 2 | |a pubmed24n1030.xml |
035 | |a (DE-627)NLM309134501 | ||
035 | |a (NLM)32329111 | ||
040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
041 | |a eng | ||
100 | 1 | |a Paprocki, Valerie |e verfasserin |4 aut | |
245 | 1 | 0 | |a Stable Actinide π Complexes of a Neutral 1,4-Diborabenzene |
264 | 1 | |c 2020 | |
336 | |a Text |b txt |2 rdacontent | ||
337 | |a ƒaComputermedien |b c |2 rdamedia | ||
338 | |a ƒa Online-Ressource |b cr |2 rdacarrier | ||
500 | |a Date Revised 12.11.2023 | ||
500 | |a published: Print-Electronic | ||
500 | |a Citation Status PubMed-not-MEDLINE | ||
520 | |a © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. | ||
520 | |a The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d-block and f-block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora-π-aromatics are less prevalent particularly for the f-block, due to less effective metal-to-ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting the exceptionally strong π donor capabilities of a neutral 1,4-diborabenzene. A series of remarkably robust, π-coordinated thorium(IV) and uranium(IV) half-sandwich complexes were synthesized by simply combining the bora-π-aromatic with ThCl4 (dme)2 or UCl4 , representing the first examples of actinide complexes with a neutral boracycle as sandwich-type ligand. Experimental and computational studies showed that the strong actinide-heteroarene interactions are predominately electrostatic in nature with distinct ligand-to-metal π donation and without significant π/δ backbonding contributions | ||
650 | 4 | |a Journal Article | |
650 | 4 | |a actinides | |
650 | 4 | |a bonding | |
650 | 4 | |a boron | |
650 | 4 | |a heterocycles | |
650 | 4 | |a π complexes | |
700 | 1 | |a Hrobárik, Peter |e verfasserin |4 aut | |
700 | 1 | |a Harriman, Katie L M |e verfasserin |4 aut | |
700 | 1 | |a Luff, Martin S |e verfasserin |4 aut | |
700 | 1 | |a Kupfer, Thomas |e verfasserin |4 aut | |
700 | 1 | |a Kaupp, Martin |e verfasserin |4 aut | |
700 | 1 | |a Murugesu, Muralee |e verfasserin |4 aut | |
700 | 1 | |a Braunschweig, Holger |e verfasserin |4 aut | |
773 | 0 | 8 | |i Enthalten in |t Angewandte Chemie (International ed. in English) |d 1964 |g 59(2020), 31 vom: 27. Juli, Seite 13109-13115 |w (DE-627)NLM000105422 |x 1521-3773 |7 nnns |
773 | 1 | 8 | |g volume:59 |g year:2020 |g number:31 |g day:27 |g month:07 |g pages:13109-13115 |
856 | 4 | 0 | |u http://dx.doi.org/10.1002/anie.202004501 |3 Volltext |
912 | |a GBV_USEFLAG_A | ||
912 | |a GBV_NLM | ||
951 | |a AR | ||
952 | |d 59 |j 2020 |e 31 |b 27 |c 07 |h 13109-13115 |